Apparatus and method for applying a film on a substrate

ABSTRACT

A system that incorporates teachings of the present disclosure may include, for example, an apparatus having a plurality of applicators, each applicator with an ingress opening to receive a liquid, and an egress opening to release the liquid, and a conductor positioned in a conduit of each of the plurality of applicators, the conductor and the conduit having dimensions to cause a surface tension of the liquid to prevent a constant flow of the liquid from the egress opening. Each conductor of the plurality of applicators can be coupled to one of one or more power sources operable to apply a charge to the liquid to overcome the surface tension and form at the egress opening of each applicator a plurality of jet sprays of the liquid applicable on a substrate to form a thin film. Additional embodiments are disclosed.

PRIOR APPLICATION

The present application claims the benefit of priority to U.S.Provisional Application No. 61/044,350 filed on Apr. 11, 2008, which ishereby incorporated herein by reference in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates generally to techniques for applying amaterial on a substrate, and more specifically to apparatuses andmethods for applying one or more materials on one or more substrates.

BACKGROUND

In an electrostatic spraying apparatus, electric charge can be suppliedto a surface of a liquid. When the repulsive forces within the liquidcaused by the electric charge exceed the surface tension maintaining thesurface of the liquid, the surface of the liquid can explosively disruptto form small jets. In some applications, the small jets can break upinto streams of charged liquid clusters in the form of nanodrops (liquidphase) or nanoparticles (solid phase formed by solidifying nanodrops).The resulting stream of nanodrops can be directed onto a surface of atarget material or substrate, which over time, can form a film on thesurface.

The charged nanodrops can collect on the surface and form a space chargebuild-up which can result in non-uniform applications of the multi-jetsprays of nanoparticles on the substrate. An electrically insulatedsubstrate cannot efficiently transport charge away from its surface.Consequently, certain areas of the substrate's surface can accumulatethe charge of the applied nanodrops. The accumulated charge can repeladditional applications of nanodrops which can cause the non-uniformapplication of nanodrops on the substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1B depict an illustrative embodiment of a material applicationapparatus;

FIGS. 2A-2D depict illustrative embodiments of an applicator portion ofthe apparatus;

FIGS. 3-10 depict illustrative embodiments of jet sprays generated bythe apparatus of FIG. 1;

FIG. 11 depicts an illustrative embodiment of a graph that describes arelationship between a number of jet sprays generated by an applicatorof the apparatus of FIG. 1 to a charge applied thereto;

FIG. 12 depicts an illustrative embodiment of the applicator of theapparatus of FIG. 1 coupled to a power source;

FIGS. 13-14 depict illustrative embodiments of housing assemblies whichcan be used to seal a portion of the apparatus of FIG. 1;

FIGS. 15A-15B depict illustrative embodiments to manage the applicationof a film on a substrate;

FIG. 16 depicts an illustrative embodiment of accessories that can beused by the apparatus of FIG. 1 to enhance and/or monitor theapplication of materials by the apparatus;

FIGS. 17-18 depict illustrative embodiments of a multi-applicatorapparatus;

FIG. 19 depicts an illustrative embodiment of a two dimensional array ofthe multi-applicator apparatus of FIGS. 17-18 arranged in a repeatedgrouping of multi-polarity applicators;

FIG. 20 depicts an illustrative embodiment of a two dimensional array of40 applicators arranged in a structure with a repeated grouping ofmulti-polarity applicators insulated from each other;

FIG. 21 depicts an illustrative embodiment of a spray pattern on asubstrate obtained with the 40-applicator apparatus of FIG. 18;

FIG. 22 depicts an illustrative embodiment of FIG. 21 with themulti-applicator structure of FIG. 19 superimposed;

FIGS. 23-24 depict illustrative embodiments of films created by theapparatuses of FIGS. 1 and 18;

FIG. 25 depicts an illustrative diagrammatic representation of a machinein the form of a computer system within which a set of instructions,when executed, may cause the machine to perform any one or more of themethodologies disclosed herein;

Tables 1-2 depict illustrations of possible embodiments of a liquid usedby the apparatus of FIGS. 1, 2, 17, or 18 for spray application on asubstrate; and

Table 3 depicts an illustrative embodiment of a PEDOT:PSS thin filmsprayed on a glass substrate showing a measured thickness of 64 pointsdistributed uniformly over the substrate.

DETAILED DESCRIPTION

One embodiment of the present disclosure entails an apparatus having aplurality of applicators, each applicator with an ingress opening toreceive a liquid, and an egress opening to release the liquid, and aconductor positioned in a conduit of each of the plurality ofapplicators, the conductor and the conduit having dimensions to cause asurface tension of the liquid to prevent a constant flow of the liquidfrom the egress opening. Each conductor of the plurality of applicatorscan be coupled to one of one or more power sources operable to apply acharge to the liquid to overcome the surface tension and form at theegress opening of each applicator a plurality of jet sprays of theliquid applicable on a substrate to form a thin film. The one or morepower sources can be operable to apply alternate charge polarities toportions of the plurality of applicators to create one or more desirednet charges for one or more corresponding portions of the thin film.

Another embodiment of the present disclosure entails an apparatus havinga plurality of applicators to receive and apply a liquid to a substrate,and a conductor positioned in a conduit of each of the plurality ofapplicators. One or more power sources can be operable to applydissimilar electrical charges to portions of the plurality ofapplicators by way of their corresponding conductors to cause eachapplicator to generate one or more jet sprays of the liquid forapplication on the substrate. One or more portions of the appliedmaterial on the substrate can have one or more corresponding net charges

Yet another embodiment of the present disclosure entails applyingdissimilar electrical charges to portions of a plurality of applicatorsby way of a conductor included in a conduit of each applicator to causeeach applicator to generate one or more jet sprays of a liquid receivedby each applicator for application on a substrate.

Another embodiment of the present disclosure entails manufacturing adevice in part by applying dissimilar electrical charges to portions ofa plurality of applicators by way of a conductor included in a conduitof each applicator to cause each applicator to generate one or more jetsprays of a liquid received by each applicator for application on acomponent of the device.

Another embodiment of the present disclosure entails a device having acomponent constructed in part by applying dissimilar electrical chargesto portions of a plurality of applicators by way of a conductor includedin a conduit of each applicator to cause each applicator to generate oneor more jet sprays of a liquid received by each applicator forapplication on the component.

Yet another embodiment of the present disclosure entails acomputer-readable storage medium having computer instructions to controlan apparatus that applies dissimilar electrical charges to portions of aplurality of applicators by way of a conductor included in a conduit ofeach applicator to cause each applicator to generate one or more jetsprays of a liquid received by each applicator for application on asubstrate.

FIGS. 1A and 2A illustrate an apparatus 10 for applying on a substrate18 a film with a multi-jet spray generated by the apparatus 10.Apparatus 10 can include generally an applicator 12 configured toreceive a liquid from reservoir 14. While referred to as reservoir 14,element 14 can also be a conduit configured to convey and/or channel asolution to be deposited from a syringe pump or other liquid injectionsource. The substrate 18 can be coupled to a stage 16 which can be movedin at least one dimension (X, Y, and/or Z) using a common linear motor,or similar mechanism.

The applicator 12 can also be attached to a similar mechanism so thatits location can be controlled on any axis (X, Y, and/or Z). The presentdisclosure contemplates that any combination of the applicator 12 andthe stage 16 can be coupled to a mechanism that controls relativepositioning between the applicator 12 and the substrate 18 attached tothe stage 16. Configuring apparatus 10 in such a manner can allow anoperator to arrange applicator 12 with sufficient proximity to substrate18 to apply film patterns of any kind.

The apparatus 10 can include processing circuitry 20 and storagecircuitry 22. Processing circuitry 20 can be coupled to either one orboth of the stage 16 and applicator 12. Processing circuitry 20 can beimplemented as a controller or other structure configured to executeinstructions including, for example, software and/or firmwareinstructions. Other example embodiments of processing circuitry 20 caninclude a desktop or laptop computer, a server, a mainframe, customizedhardware logic, and/or in structures such as a PGA, FPGA, or ASICconfigured for controlling operations of the apparatus 10.

The processing circuitry 20 can be configured to control the operationalparameters of the applicator 12 and the stage component 16. Configurableparameters of the applicator 12 and stage 16 can include the chargedensity of the liquid, the flow rate of the liquid traveling through theapplicator 12, monitoring the viscosity and the dielectric constant ofthe liquid flowing through applicator 12, relative positioning of theapplicator 12 and the substrate 18 held by the stage 16, temperaturecontrol of the substrate 18 by way of a common temperature controldevice, and so on.

Processing circuitry 20 can also be configured to store and access datafrom storage circuitry 22. Storage circuitry 22 can be configured tostore in a processor useable media electronic data and/or programmingdata such as executable instructions (e.g., software and/or firmware),or other digital information. Processor useable media can include anyarticle of manufacture which can contain, store, or maintainprogramming, data, and/or other digital information for use by or inconnection with an instruction execution system such as the processingcircuitry 20.

For example, processor useable media may include any one of physicalmedia such as electronic, magnetic, optical, electromagnetic, orsemiconductor storage media. Some specific examples of processor useablemedia include, but are not limited to, a portable magnetic computerdiskette, such as a floppy diskette, zip disc, hard drive, random accessmemory, read only memory, flash memory, cache memory, and/or otherconfigurations capable of storing programming instructions, data, orother digital information.

Storage circuitry 22 can for example be used to store a plurality ofdata sets. These data sets can include specific parameters for specificsubstrates and liquids being deposited on the substrates. For example,in certain instances where a film of silver is deposited from a silverliquid solution from reservoir 14 via applicator 12 over a glasssubstrate 18, storage circuitry 22 can include a data set specific toany combination of deposition parameters. These parameters can include,for example, the type of solution, the type of substrate, the desiredpattern, the flow rate parameter, a liquid charge density parameter,temperature control of the substrate, and so on.

FIGS. 2A-2D describe embodiments of a portion of the applicator 12operating as a nozzle 50 for depositing and/or applying a film ofmaterial on a substrate 18 by way of multi-jet sprays 37. The nozzle 50can include a tube 30 such as a capillary tube having a conduit 43 withan ingress opening 45 and an egress opening 33. The capillary tube canbe of insulating material. The ingress opening 45 can be coupled to thereservoir 14 of FIG. 1A or another form of a fluid delivery device suchas a syringe pump for directing liquid 31 through the tube 30 (see FIG.16).

An electrical conductor 40 can be positioned in the conduit 43 of thetube 30 in a variety of ways to control the charge density of the liquid31. The conductor 40 can be of any material with conductive propertiesfor applying a charge to the liquid 31. In an embodiment, the electricalconductor 40 can be in the form of a hollow cylinder 41 such as a“sleeve” (herein referred to as sleeve 41) illustrated by thecross-section of FIG. 2A. The sleeve 41 can be co-axially positioned inthe conduit 43 so that some of the liquid 31 travels within the innerwalls of the sleeve 41 and a portion travels between the sleeve 41 andthe conduit 43. Although the sleeve 41 is shown to have an axial lengthand positioning that does not extend from the ingress opening 33, otherembodiments are possible.

For instance, the sleeve 41 can be shorter than what is shown in FIG.2A, or it can be longer. The sleeve 41 can reach or extend beyond theegress opening 33 as shown by the dashed lines. The sleeve 41 can have awider or narrower diameter than is shown. The sleeve 41 does not have tobe co-axially positioned in the conduit 43, it can be positioned closerto one side of the conduit 43 than the other. The thickness of the wallsof the sleeve 41 can be thick or thin. Any number of suitableembodiments of the sleeve 41 are applicable to the present disclosure.

In another embodiment, the electrical conductor 40 can be in the form ofa hollow cylinder 42 such as a “sleeve” (herein referred to as sleeve42) coupled to the inside walls of the conduit 43 of the tube 30 asillustrated by the cross-section of FIG. 2B. Similar to the previousembodiment, the sleeve 42 can be coaxially positioned in the conduit 43or with an offset, have an axial length less than or extending from theegress opening 33 (see dashed lines), have a variety of thicknesses, andso on.

Each of the applicators 12 of FIGS. 2A-2B can also include electricalinsulators 35. Insulator 35 can be grounded for example to insulate theapplicator 12 from other applicators 12 of a dissimilar voltagepotential. Insulator 35 of one applicator 12 prevents cross coupling ofelectric fields generated thereby with the electric fields ofneighboring applicators 12. By electrically isolating each applicator 12from its neighbors the multi-jet spray 37 of each applicator 12 canoperate independently without influence from its neighboring applicators12 which may be operating with one or more dissimilar charges.

In yet another embodiment, the electrical conductor 40 can be in theform of a solid conductor 32 as shown by cross-sections in FIGS. 2C-2D.The solid conductor 32 can be a thin diameter electrode made of forexample tungsten with a nano-sharp needle tip, a partially blunt tip, orblunt tip. The length, positioning of the conduit 43, and thickness ofthe solid conductor 32 can be varied. Similar to the embodiments ofFIGS. 2A-2B, the applicators 12 of FIGS. 2C-2D can utilize electricalinsulators 35 to minimize electric field influences from neighboringapplicators 12 operating with dissimilar electric charges.

The electric field emitted from the tip of the solid conductor 40 can beproportional to a ratio of the voltage applied to the conductor 40 andthe diameter of the tip of the conductor 40. Under a condition forexample where the voltage applied to the solid conductor 40 is constant,the electric field generated by the tip of a nano-sharp needle will begreater than the electric field generated by a blunt tip of a greaterdiameter. Accordingly, a nano-sharp needle conductor 40 can provideoperational benefits in managing the charge density of a precursorsolution flowing through the tube 30.

Although not shown, the foregoing embodiments can be combined. Forinstance the solid conductor of FIGS. 2C-2D can be combined with one ofthe sleeves 41 and 42 of FIGS. 2A or 2B. In this embodiment, the solidconductor 32 can be surrounded by one of sleeves 41 and 42. In yetanother embodiment, the sleeves 41 and 42 can be combined as concentricsleeves.

It should be evident from the above illustrations that the conductor 40can have numerous embodiments, and that there can also be numerousplacements of the conductor 40 in the conduit 43. These non-disclosedembodiments are contemplated by the present disclosure.

The conductor 40 illustrated in FIGS. 2A-2D can be coupled by wire toone or more high voltage power supplies (see FIG. 12). A stable andrepeatable multi-jet spray 37 can be applied to a substrate 18 bycontrolling the voltage applied to the conductor 40, the flow rate ofthe liquid 31 through the tube 30, the viscosity of the liquid and thedielectric constant of the solution, and the surface tension of theliquid 31, just to mention a few controllable parameters. Under theright parametric conditions, a stable multi-jet spray 37 can emanatesuch as to enable the applicator 12 to “consistently” apply desirablespray patterns on substrate 18.

Before an electrical charge is applied to the conductor 40, the liquid31 can protrude from the egress opening 33 of the nozzle 50 in the formof a drop. The viscosity and surface tension properties (F_(γ)) of theliquid can prevent it from causing a continuous flow from the egressopening 33 while the conductor 40 is in a neutral state. As a charge isapplied to the liquid 31 by way of conductor 40, Coulomb repulsionforces caused by the surface charges on the liquid (F_(electr.)) opposethe surface tension forces. With increasing charge density, a multi-jetspray 37 can be caused to emanate from the tube 30. The multi-jet spray37 can be stabilized by selecting a desired viscosity and dielectricconstant for the liquid 31, and controlling the flow rate of saidsolution through the tube 30.

FIGS. 3-10 provide several illustrations of a stable multi-jet spray 37produced repeatedly in a stable manner by the applicators 12 of FIGS.2A-2D. FIGS. 3-10 show how the applicator 12 can be controlled togenerate as few as three evenly spaced jet sprays to 16 evenly jetsprays. FIG. 11 illustrates a graph depicting a relationship between anumber of jet sprays produced by the applicator 12 as a result of acharge applied to the conductor 40 of the applicator 12. FIG. 11 showsthat as the charge applied to the conductor 40 is raised the number ofjet sprays generated by the applicator 12 increases in an approximatelylinear fashion (I^(5/4)). The radius (R) of the charged drops created bythe jet spray can be determined as a function of current (I) and flowrate (Q) as follows:

${R = {\left( {36ɛ\; T} \right)^{1/3}\left( \frac{Q}{I} \right)^{2/3}}},$

where ε is the permittivity of the liquid, and T is the surface tensionof the liquid The number of jet sprays (N) as a function of I and Q canbe described by:

$\begin{matrix}{N = {\left( \frac{\rho \; r^{12}}{2^{34}3^{5}\pi^{2}ɛ^{5}T^{6}} \right)^{1/8}I^{5/4}Q^{- 1}}} \\{\approx {0.019867\left( \frac{\rho \; r^{12}}{ɛ^{5}T^{6}} \right)^{1/8}I^{5/4}Q^{- 1}}}\end{matrix}$

where ρ is the mass density of the liquid and r is the radius of theegress opening 33 of the nozzle 50.

Referring back to FIG. 2, the liquid 31 can comprise a precursorsolution of a variety of materials such as metals, metalorganiccompounds, metal salts, sol-gel processed materials, ceramics, polymers,oligomers, oxides, hydroxides, hydrides, and/or one or more solventscombined with any of these materials. Some materials such as polymerscan be heated to a molten state if a solvent is not desirable for aparticular application. Surfactants can also be used to vary the surfacetension of the precursor solution. Binders such as polyethylene glycoland ethyl cellulose can also be used to vary the viscosity of theprecursor solution to thereby maintain a pattern structure applied tothe substrate 18 that can be later removed using heat treatment. Otherbinders are possible.

Metals can include for example silver or nickel from metalorganicprecursors in solvent, silver from Dupont Fodel screen printable pastecontaining silver nanoparticles, or platinum from a precursor inSolaronix pastes. Polymers can include functional polymers such asPEDOT:PSS, P3HT or other polymers dispersed in solvent. Oxides caninclude titanium dioxide (TiO₂), titanium oxynitride (TiON) frommetalorganic precursors in solvent, TiO₂ nanoparticle networks fromSolaronix screen printable pastes, nickel oxide from metalorganicprecursors in solvent, dielectric glass, or low-temperature glass fromscreen printable pastes.

The precursor solution can also comprise biomaterials and biologicalmaterials. For instance, the precursor solution can comprise a solutionof chitosan, gelatin, alginate, agarose, peptides, proteins, therapeuticagents, cells, and DNA or protein molecules dispersed in solvent.

By choosing an appropriate precursor solution, the apparatus 10 cancreate films and nanoparticle applications of varying thicknesses,sizes, chemical compositions and stoichiometries.

The precursor solution created in any of these instances can also becontrolled for a desired viscosity, conductivity, dielectric constantand surface tension. Table 1 provides an illustration of precursorsolutions that can be used for application on a substrate 18. Table 2further illustrates materials that have been deposited by apparatus 10of FIGS. 1, 2, 17, or 18. It should be noted that Tables 1 and 2 areillustrative and non-limiting as it would be apparent to an artisan withordinary skill in the art that there are nearly limitless materialsolutions possible that can be utilized by apparatus 10 for sprayapplications. Other material solutions are therefore contemplated by thepresent disclosure.

There are also nearly limitless operational factors of the apparatus 10which can be intentionally altered to create varied results in the jetsprays generated by the applicator 12 of the apparatus 10. Theseoperational factors can include, for example, the flow rate of theprecursor solution through the tube 30, the surface charge densitycreated by the amount of charge applied by the conductor 40 controllablewith a programmable power supply, the distance between the substrate 18and the egress opening 33 (referred to herein as meniscus distance 36),and the multi-planar (1D, 2D or 3D) motion between the substrate 18 andthe one or more jet sprays generated by the applicator 12. With so manycombinations of precursor solutions and operation characteristics of theapparatus 10, innumerable film patterns can be applied to substrate 18.

The spray patterns generated by apparatus 10 can vary in thickness,material characteristics (e.g., resistivity, vertical height, patternspreading, other geometries), format (e.g., contiguous patterns,patterns with discontinuities), and so on. FIGS. 23-24 provideillustrative films created by the apparatus 10 of FIGS. 2A-2D. As shownin FIGS. 23-24, apparatus 10 of FIG. 2 can be used to fabricate thinfilms, nanoparticles, and nanofibers of desired sizes. Apparatus 10 islargely insensitive to the choice of materials and is scalable.Accordingly, other spray patterns are possible and contemplated by thepresent disclosure.

A housing assembly can be added to a portion of the apparatus 10 asshown in FIGS. 13 and 14. The housing assembly can be used to apply agas or fluid for controlling a temperature of the precursor solution asit is being applied. The housing assembly can also be adapted to providea hermetic seal with a portion of the nozzle 50 and the substrate 18(not shown in FIGS. 13 or 14). With a common pump or other mechanicalextraction device, air and/or other gases can be extracted from theassembly to create a near vacuum seal. The housing assembly can be usedin applications where environmental control of the application ofprecursor solutions is desirable.

Other accessory devices can be used with apparatus 10 to control itsoperational characteristics. For example, a common temperatureapplication device can be coupled to the substrate 18 to either heat orcool the substrate 18 during material application. In yet anotherembodiment, an electrical or electromechanical shutter system as shownin FIGS. 15A and 15B, respectively, can be used to generatediscontinuous patterns at high speed. The electrical shutter system canrely on the surface tension of the precursor solution to preventcontinuous flow when the conductor 40 is in a neutral charge state,while the electromechanical shutter can combine both the electricalshutter concept with a mechanical shutter that can be controlled toobstruct or enable application with a common actuator mechanism.

Several operational devices can be added to the apparatus 10 for qualitycontrol. For instance, a thermal sensor can be used to measure thetemperature of the substrate 18 and/or the precursor solution duringapplication. The thermal sensor can be a common temperature sensorcoupled to substrate 18, or an infrared sensor that can measure thetemperature of the precursor solution while being applied. Additionally,an imaging sensor such as a microscope camera can be used to monitor theapplication process for accuracy. These additional components are shownin FIG. 16.

The apparatus 10 can also be adapted to have a plurality of nozzles 82as shown in FIG. 17. The plurality of nozzles 82 can share a commonreservoir 84, or each nozzle can be coupled to an independent fluidinjection device, each providing a unique precursor solution managed bythe processing circuitry 20 discussed previously. The plurality ofnozzles 82 can generate multi-jet sprays that can be appliedsynchronously or asynchronously between nozzles to form a variety ofspray patterns on a single substrate 88 controlled by a staging device86. Alternatively, the plurality of nozzles 82 can be used to applyspray patterns on a plurality of substrates each individually controlledby its own stage. In yet another embodiment, portions of the pluralityof nozzles 82 can also be coupled to a staging device so that thenozzles and/or the substrate can be moved relative to each other in anydirection as described earlier for the apparatus of FIG. 1B. FIG. 18illustrates an apparatus 10 with 40 nozzles each coupled to a syringepump.

It should be evident from the abovementioned operational characteristicsof the apparatus 10 with a single nozzle (or multiplicity of nozzles)that there can be endless operational configurations of the apparatus 10which can control the application of materials on one or moresubstrates. It would be impractical to describe all the possibleembodiments in the present disclosure. Nevertheless, these non-disclosedembodiments are contemplated and therefore considered relevant to thepotential use of the apparatus 10 as described herein.

The multi-applicator apparatus 10 of FIG. 18 can be adapted to applyprecursor solutions on a substrate with one or more net charges. Toaccomplish this, the 40 applicators 12 of the apparatus 10 of FIG. 18can be arranged for example in a two dimensional array as shown in FIGS.19-20. In addition, the array can be arranged with repeatable groups ofapplicators 12 which can produce one or more jet sprays of varyingpolarity per applicator 12 in response to one or more power suppliesvarying the applied voltage of these applicators 12 groups. In thisillustration, for example, two applicators 12 generate one or more jetsprays at one polarity while the other two applicators 12 generate oneor more jet sprays of an opposing polarity.

With this arrangement precursor nanodrops generated by themulti-polarity jet sprays repel each other, and can be controlled toapply on a substrate a uniform conformal coating of films ornanoparticles of substantially a neutral net charge. Such applicationscan take place on flat or curved surfaces with three dimensionalstructures. The apparatus 10 of FIG. 18 can be adapted to move thesubstrate in its own plane such that any point on the substraterepresents an average in time over a region covered by a group ofmulti-polarity jet sprays thus enabling uniform deposition of the liquidthroughout the substrate to form a thin film. An illustration of such anapplication is shown in FIG. 21 with the multi-applicator structure ofFIG. 19 superimposed thereon in FIG. 22. Although there are gaps betweenthe film applications of FIG. 21, the substrate and/or the applicators12 of FIG. 18 can be moved relative to each other to create a thincontinuous film of substantially a neutral net charge.

It would be apparent to an artisan with ordinary skill in the art thatother arrangements other than the structure of FIGS. 19-22 can be used.It would also be apparent to said artisan that it may be desirable tocreate portions of the substrate with varying net charges. This latterembodiment can be accomplished by varying the charge applied to portionsof the applicators 12. The dissimilar charges do not have to be ofopposing polarities. For instance, positive charges of different voltagepotentials can be applied to a number of the applicator 12 groups in thestructure of FIG. 19 to create portions of an application on thesubstrate with one or more net charges.

Accordingly, one portion can have a net positive charge that is higheror lower than a neighboring portion created by another applicator group.Any combination of positive or negative net charges can be created on aper applicator basis or by desired applicator group patterns. Byelectrically insulating each applicator 12 in any suitable arrangement,each applicator 12 is prevented from electrostatically influencingneighboring applicators so that any charged jet spray combination ispossible.

With an arrangement such as in FIGS. 18-20 applications can be carriedout on large substrates in a short period of time with a high degree ofrepeatability. Table 3 shows thickness variation in a PEDOT:PSS thinfilm deposited using the 40-nozzle array of FIG. 18 over a 12″×12″ glasssubstrate. The height units in Table 3 are in angstroms. Thin filmthickness is measured at 64 points distributed uniformly over the glasssubstrate. For a mean thickness of 308 nm, the standard deviation inthickness is approximately 10% of the mean. It should be evident fromthe results of Table 3 (and the illustrations of Tables 1-2 and FIGS.23-24) that highly uniform applications of various sizes, materials andstructures are possible.

It would be apparent to an artisan with ordinary skill in the art afterreviewing the above disclosure that any of the foregoing embodiments canbe adapted in numerous ways without departing from the scope and spiritof the claims described below. Accordingly, the reader is directed tothe claims for a fuller understanding of the breadth and scope of thepresent disclosure.

FIG. 25 depicts an illustrative diagrammatic representation of a machinein the form of a computer system 2500 within which a set ofinstructions, when executed, may cause the machine to perform any one ormore of the methodologies discussed above on the apparatus 10 and/or itsperipherals. In some embodiments, the machine operates as a standalonedevice. In some embodiments, the machine may be connected (e.g., using anetwork) to other machines. In a networked deployment, the machine mayoperate in the capacity of a server or a client user machine inserver-client user network environment, or as a peer machine in apeer-to-peer (or distributed) network environment.

The machine may comprise a server computer, a client user computer, apersonal computer (PC), a tablet PC, a laptop computer, a desktopcomputer, a control system, a network router, switch or bridge, or anymachine capable of executing a set of instructions (sequential orotherwise) that specify actions to be taken by that machine. It will beunderstood that a device of the present disclosure includes broadly anyelectronic device that provides voice, video or data communication.Further, while a single machine is illustrated, the term “machine” shallalso be taken to include any collection of machines that individually orjointly execute a set (or multiple sets) of instructions to perform anyone or more of the methodologies discussed herein.

The computer system 2500 may include a processor 2502 (e.g., a centralprocessing unit (CPU), a graphics processing unit (GPU, or both), a mainmemory 2504 and a static memory 2506, which communicate with each othervia a bus 2508. The computer system 2500 may further include a videodisplay unit 2510 (e.g., a liquid crystal display (LCD), a flat panel, asolid state display, or a cathode ray tube (CRT)). The computer system2500 may include an input device 2512 (e.g., a keyboard), a cursorcontrol device 2514 (e.g., a mouse), a disk drive unit 2516, a signalgeneration device 2518 (e.g., a speaker or remote control) and a networkinterface device 2520.

The disk drive unit 2516 may include a machine-readable medium 2522 onwhich is stored one or more sets of instructions (e.g., software 2524)embodying any one or more of the methodologies or functions describedherein, including those methods illustrated above. The instructions 2524may also reside, completely or at least partially, within the mainmemory 2504, the static memory 2506, and/or within the processor 2502during execution thereof by the computer system 2500. The main memory2504 and the processor 2502 also may constitute machine-readable media.

Dedicated hardware implementations including, but not limited to,application specific integrated circuits, programmable logic arrays andother hardware devices can likewise be constructed to implement themethods described herein. Applications that may include the apparatusand systems of various embodiments broadly include a variety ofelectronic and computer systems. Some embodiments implement functions intwo or more specific interconnected hardware modules or devices withrelated control and data signals communicated between and through themodules, or as portions of an application-specific integrated circuit.Thus, the example system is applicable to software, firmware, andhardware implementations.

In accordance with various embodiments of the present disclosure, themethods described herein are intended for operation as software programsrunning on a computer processor. Furthermore, software implementationscan include, but not limited to, distributed processing orcomponent/object distributed processing, parallel processing, or virtualmachine processing can also be constructed to implement the methodsdescribed herein.

The present disclosure contemplates a machine readable medium containinginstructions 2524, or that which receives and executes instructions 2524from a propagated signal so that a device connected to a networkenvironment 2526 can send or receive voice, video or data, and tocommunicate over the network 2526 using the instructions 2524. Theinstructions 2524 may further be transmitted or received over a network2526 via the network interface device 2520.

While the machine-readable medium 2522 is shown in an example embodimentto be a single medium, the term “machine-readable medium” should betaken to include a single medium or multiple media (e.g., a centralizedor distributed database, and/or associated caches and servers) thatstore the one or more sets of instructions. The term “machine-readablemedium” shall also be taken to include any medium that is capable ofstoring, encoding or carrying a set of instructions for execution by themachine and that cause the machine to perform any one or more of themethodologies of the present disclosure.

The term “machine-readable medium” shall accordingly be taken toinclude, but not be limited to: solid-state memories such as a memorycard or other package that houses one or more read-only (non-volatile)memories, random access memories, or other re-writable (volatile)memories; magneto-optical or optical medium such as a disk or tape; andcarrier wave signals such as a signal embodying computer instructions ina transmission medium; and/or a digital file attachment to e-mail orother self-contained information archive or set of archives isconsidered a distribution medium equivalent to a tangible storagemedium. Accordingly, the disclosure is considered to include any one ormore of a machine-readable medium or a distribution medium, as listedherein and including art-recognized equivalents and successor media, inwhich the software implementations herein are stored.

Although the present specification describes components and functionsimplemented in the embodiments with reference to particular standardsand protocols, the disclosure is not limited to such standards andprotocols. Each of the standards for Internet and other packet switchednetwork transmission (e.g., TCP/IP, UDP/IP, HTML, HTTP) representexamples of the state of the art. Such standards are periodicallysuperseded by faster or more efficient equivalents having essentiallythe same functions. Accordingly, replacement standards and protocolshaving the same functions are considered equivalents.

The illustrations of embodiments described herein are intended toprovide a general understanding of the structure of various embodiments,and they are not intended to serve as a complete description of all theelements and features of apparatus and systems that might make use ofthe structures described herein. Many other embodiments will be apparentto those of skill in the art upon reviewing the above description. Otherembodiments may be utilized and derived therefrom, such that structuraland logical substitutions and changes may be made without departing fromthe scope of this disclosure. Figures are also merely representationaland may not be drawn to scale. Certain proportions thereof may beexaggerated, while others may be minimized. Accordingly, thespecification and drawings are to be regarded in an illustrative ratherthan a restrictive sense.

Such embodiments of the inventive subject matter may be referred toherein, individually and/or collectively, by the term “invention” merelyfor convenience and without intending to voluntarily limit the scope ofthis application to any single invention or inventive concept if morethan one is in fact disclosed. Thus, although specific embodiments havebeen illustrated and described herein, it should be appreciated that anyarrangement calculated to achieve the same purpose may be substitutedfor the specific embodiments shown. This disclosure is intended to coverany and all adaptations or variations of various embodiments.Combinations of the above embodiments, and other embodiments notspecifically described herein, will be apparent to those of skill in theart upon reviewing the above description.

The Abstract of the Disclosure is provided to comply with 37 C.F.R.§1.72(b), requiring an abstract that will allow the reader to quicklyascertain the nature of the technical disclosure. It is submitted withthe understanding that it will not be used to interpret or limit thescope or meaning of the claims. In addition, in the foregoing DetailedDescription, it can be seen that various features are grouped togetherin a single embodiment for the purpose of streamlining the disclosure.This method of disclosure is not to be interpreted as reflecting anintention that the claimed embodiments require more features than areexpressly recited in each claim. Rather, as the following claimsreflect, inventive subject matter lies in less than all features of asingle disclosed embodiment. Thus the following claims are herebyincorporated into the Detailed Description, with each claim standing onits own as a separately claimed subject matter.

TABLE 1 Solution Concentration Nature of (mole/L) Solute Solvent ProductProduct 1 0.1 M Zn-trifluoroacetate Methanol ZnO piezoelectric,semiconductor thin films 2 0.1 M Y-trifluoroacetate Methanol YBa₂Cu₃O₇superconductor 0.2 M Ba-trifluoroacetate thin films 0.3 MCu-trifluoroacetate 3 0.1 M Pd-trifluoroacetate Water Pd metallicnanoparticles 4 0.1 M Ta-ethoxide Methanol Ta₂O₅ insulator, thin filmsand nanoparticles 5 0.1 M Ag-trifluoroacetate Methanol Ag metallicnanoparticles 6 0.1 M Pd-trifluoroacetate Methanol Pd_(0.5)Ag_(0.5)inter-metallic 0.1 M Ag-trifluoroacetate Methanol nanoparticles

TABLE 2 BaTiO₃, SrTiO₃, BST, ZnO, Iron Oxide, NiO, Cobalt Oxide, PZT,PZN, MgO, TiO₂, TiON, SiO₂, Al₂O₃, Mn-doped Zn₂SiO₄, Cu, Ag, Ni, Pd,PVA, MgF₂, CaF₂, PEDOT, GCP, Other polymers

1. An apparatus, comprising: a plurality of applicators, each applicator with an ingress opening to receive a liquid, and an egress opening to release the liquid; and a conductor positioned in a conduit of each of the plurality of applicators, the conductor and the conduit having dimensions to cause a surface tension of the liquid to prevent a constant flow of the liquid from the egress opening; wherein each conductor of the plurality of applicators is coupled to one of one or more power sources operable to apply a charge to the liquid to overcome the surface tension and form at the egress opening of each applicator a plurality of jet sprays of the liquid applicable on a substrate to form a thin film, and wherein the one or more power sources are operable to apply alternate charge polarities to portions of the plurality of applicators to create one or more desired net charges for one or more corresponding portions of the thin film.
 2. The apparatus of claim 1, wherein each applicator comprises one of a tube and a nozzle.
 3. The apparatus of claim 1, wherein the plurality of applicators are arranged in a two dimensional array of applicators.
 4. The apparatus of claim 3, wherein the two dimensional array of applicators are arranged in periodic groups of multi-polarity applicators to create an electric field distribution.
 5. The apparatus of claim 1, wherein each applicator is insulated to prevent electrostatic influence by neighboring applicators of opposite polarity.
 6. The apparatus of claim 1, wherein the substrate is one of a conducting substrate and insulating substrate.
 7. The apparatus of claim 1, wherein the liquid comprises a precursor solution, and wherein the precursor solution comprises at least one of a metal, a metal compound, a sol-gel processed material, a polymer, an oligomer, an oxide, a ceramic, an organic material, a biomaterial, a biological material, and a solvent combined with at least one thereof.
 8. The apparatus of claim 1, wherein the conductor of each applicator comprises a solid conductor.
 9. The apparatus of claim 8, wherein the solid conductor comprises a nano-sharpened tungsten electrode.
 10. The apparatus of claim 1, wherein the conductor of each applicator is a sleeve positioned in the applicator, wherein a diameter of the sleeve results in one of the outer surface of the sleeve contacting the surface of the conduit, and outer surface of the sleeve having a separation from the surface of the conduit of the applicator.
 11. The apparatus of claim 1, comprising a position altering apparatus coupled to the substrate to shift the substrate in at least one plane.
 12. The apparatus of claim 11, wherein the position altering apparatus is adaptable to move the substrate in the at least one plane such that that any point on the substrate represents an average in time over a region covered by a group of multi-polarity jet sprays thus enabling uniform deposition of the liquid throughout the substrate to form the thin film.
 13. The apparatus of claim 1, comprising a position altering apparatus coupled to the plurality of applicators to shift the plurality of applicators in at least one plane.
 14. The apparatus of claim 13, wherein the position altering apparatus is adaptable to move the plurality of applicators in the at least one plane such that any point on the substrate represents an average in time over a region covered by a group of multi-polarity jet sprays thus enabling uniform deposition of the liquid throughout the substrate to form the thin film.
 15. The apparatus of claim 1, wherein the plurality of applicators generate multi-polarity jet sprays that breakup into multi-polarity nanodrops.
 16. The apparatus of claim 15, wherein electrostatic forces between the multi-polarity nanodrops produce a nearly homogeneous coating to form the thin film.
 17. The apparatus of claim 15, wherein the plurality of applicators are adaptable to apply the multi-polarity jet sprays without a vacuum.
 18. The apparatus of claim 1, wherein the thin film is adaptable to one of pyrolysis and annealing.
 19. The apparatus of claim 1, comprising one of a reservoir and a device to propel the liquid into each of the plurality of applicators.
 20. The apparatus of claim 1, wherein the constant flow of the liquid in each applicator is prevented by the surface tension of the liquid and its viscosity while the conductor of each applicator is approximately electrically neutral.
 21. The apparatus of claim 1, wherein the alternate charge polarities comprise at least one of alternate charge polarities of the same magnitude and alternate charge polarities of varying magnitudes.
 22. The apparatus of claim 1, wherein the thin film comprises one of a continuous film and a particulate film.
 23. The apparatus of claim 1, comprising an imaging system to determine the application of the multi-jet spray on the substrate by at least a portion of the plurality of applicators.
 24. The apparatus of claim 1, comprising a temperature application device coupled to at least a portion of the apparatus to control a temperature of at least one of the substrate and the multi-jet spray of at least a portion of the plurality of applicators.
 25. The apparatus of claim 24, comprising a thermal sensor device to sense the temperature of at least one of the substrate and the multi-jet spray of at least a portion of the plurality of applicators.
 26. The apparatus of claim 1, comprising a removable obstruction to obstruct an application of the liquid to the substrate, wherein the removable obstruction comprises a shutter controllable by an actuator to cause an obstruction of the application of the liquid to the substrate, or to cause a removal of the obstruction of the application of the liquid to the substrate.
 27. The apparatus of claim 1, comprising a controller to cause the apparatus to synchronously or asynchronously generate a plurality of multi-jet sprays applicable on the substrate.
 28. An apparatus, comprising: a plurality of applicators to receive and apply a liquid to a substrate; and a conductor positioned in a conduit of each of the plurality of applicators, wherein one or more power sources are operable to apply dissimilar electrical charges to portions of the plurality of applicators by way of their corresponding conductors to cause each applicator to generate one or more jet sprays of the liquid for application on the substrate, wherein one or more portions of the applied material on the substrate have one or more corresponding net charges.
 29. A method, comprising applying dissimilar electrical charges to portions of a plurality of applicators by way of a conductor included in a conduit of each applicator to cause each applicator to generate one or more jet sprays of a liquid received by each applicator for application on a substrate, wherein one or more portions of the applied material on the substrate have one or more corresponding net charges.
 30. The method of claim 29, comprising controlling the net charges of the one or more portions of the film according to a setting of the dissimilar electrical charges.
 31. A method, comprising manufacturing a device in part by applying dissimilar electrical charges to portions of a plurality of applicators by way of a conductor included in a conduit of each applicator to cause each applicator to generate one or more jet sprays of a liquid received by each applicator for application on a component of the device, wherein one or more portions of the applied material on the component have one or more corresponding net charges.
 32. The method of claim 31, wherein the device comprises one of a computer, a display, an integrated circuit, a printed circuit board, a wafer, or portions thereof.
 33. A device, comprising a component constructed in part by applying dissimilar electrical charges to portions of a plurality of applicators by way of a conductor included in a conduit of each applicator to cause each applicator to generate one or more jet sprays of a liquid received by each applicator for application on the component, wherein one or more portions of the applied material on the component have one or more corresponding net charges.
 34. A computer-readable storage medium, comprising computer instructions to control an apparatus that applies dissimilar electrical charges to portions of a plurality of applicators by way of a conductor included in a conduit of each applicator to cause each applicator to generate one or more jet sprays of a liquid received by each applicator for application on a substrate, wherein one or more portions of the applied material on the substrate have one or more corresponding net charges. 